S,S′-bis-(α, α′-Disubstituted-α″-Acetic acid)—trithiocarbonates and derivatives as initiator—chain transfer agent—terminator for controlled radical polymerizations and the process for making the same

ABSTRACT

A s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate and derivatives thereof can be used as an initiator, chain transfer agent, or terminator for polymerization of monomers such as free radical polymerizable monomers. Homopolymers, copolymers, and the like as well as block copolymers can be made utilizing the trithio carbonate compound such as in a living free radical polymerization as well as to form telechelic polymers.

This application is a divisional application of copending U.S.application Ser. No. 11/192,282 filed on Jul. 28, 2005, which is adivisional application of U.S. application Ser. No. 10/429,323, filed onMay 5, 2003, now U.S. Pat. No. 6,962,961, which is a divisionalapplication of U.S. application Ser. No. 09/505,749 filed on Feb. 16,2000, now U.S. Pat. No. 6,596,899.

FIELD OF THE INVENTION

The present invention relates to s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates and derivatives thereof, as well as a processfor making the same. Moreover, other functional end groups can bederived from the carboxylic acid end groups. The compounds can beutilized as initiators, chain transfer agents, or terminators forcontrolled free radical polymerizations. Free radical polymerizationsutilizing s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompounds generally form telechelic polymers. If an initiator other thanthe s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompound is also utilized, a polymer having a single functional endgroup is formed in proportion to the amount of the initiator to thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundutilized.

BACKGROUND OF THE INVENTION

Although several members of the class of organic thiocarbonates havebeen known for many years and various routes have been employed fortheir synthesis, the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds of the present invention have not beendisclosed. Trithiocarbonate compounds have been claimed for variousapplications, such as pesticides for agriculture, and also aslubricating oil additives.

Traditional methods of producing block copolymers, such as by livingpolymerization or the linking of end functional polymers, suffer manydisadvantages, such as the restricted type monomers which can beutilized, low conversion rates, strict requirements on reactionconditions, and monomer purity. Difficulties associated with end linkingmethods include conducting reactions between polymers, and problems ofproducing a desired pure end functional polymer. Thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention can alleviate the above noted problems anddifficulties when utilized in free radical polymerizations.

The prior art WO98/01478 reference discloses the use of thiocarbonatesto conduct living free radical polymerizations. The reference is limitedto alkyl and benzyl functional groups, and is unable to make any aryl orcarboxylic acid substituted trithiocarbonates with general methods knownto the art. Synthesis, p 894 (1986), J. Chemical Research (Synopsis), p478 (1995), and Synthetic Communications, Vol. 18, p 1531 (1988). Wehave also found the conversion for the dibenzyl derivatives disclosed intheir example 26 to be very slow compared to the present invention whenpolymerizing acrylate, as can be seen in the Example section of thisapplication.

SUMMARY OF THE INVENTION

The present invention relates to s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates which have the general formula:

where R¹ and R² are set forth below, to derivatives thereof, and to aprocess for making the same.

The s,s′-bis-(α,α′-disubstituted-α″-acetic acid) trithiocarbonatecompounds can generally be formed from carbon disulfide, a haloform, anda ketone in a strong base, such as sodium hydroxide, followed byacidification. The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)trithiocarbonate compounds can be used as inifertors, i.e. as initiatorsand chain transfer agents, and/or chain terminators or as achain-transfer agent during polymerization. The compounds can thus beutilized to control free radical polymerization thermally and chemicallyto give narrow molecular weight distributions. Polymerization ofmonomers can be in bulk, in emulsion, or in solution. Block copolymerscan be made if two or more monomers are polymerized in succession. Thedifunctional acid end groups present can further react with otherreactive polymers or monomers to form block or random copolymers. Freeradical polymerizations utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsgenerally form telechelic polymers. If an initiator other than thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundis also utilized, a polymer having a single functional end group isformed in proportion to the amount of said other initiator to thes,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundutilized.

DETAILED DESCRIPTION OF THE INVENTION

The s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate andderivatives prepared by the processes disclosed later herein generallycan be described by the formula:

wherein R¹ and R², independently, can be the same or different, and canbe linear or branched alkyls having from 1 to about 6 carbon atoms, or aC₁ to about C₆ alkyl having one or more substituents, or one or morearyls or a substituted aryl group having 1 to 6 substituents on the arylring, where the one or more substituents, independently, comprise analkyl having from 1 to 6 carbon atoms; or an aryl; or a halogen such asfluorine or chlorine; or a cyano group; or an ether having a total offrom 2 to about 20 carbon atoms such as methoxy, or hexanoxy; or anitro; or combinations thereof. Examples of such compounds includes,s′-bis-2-methyl-2-propanoic acid-trithiocarbonate ands,s′-bis-(2-phenyl-2-propanoic acid)-trithiocarbonate. R¹ and R² canalso form or be a part of a cyclic ring having from 5 to about 12 totalcarbon atoms. R¹ and R² are preferably, independently, methyl or phenylgroups.

The abbreviated reaction formula for thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates of thepresent invention can be generally written as follows:

The process utilized to form the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds of the present invention is generally amulti-step process and includes combining the carbon disulfide and abase whereby an intermediate trithio structure is formed, see I, II,III, and IV. Ketone can serve as solvent for the carbon disulfide/basereaction and thus can be added in the first step of the reaction. In thesecond step of the reaction, the haloform, or haloform and ketone, or aα-trihalomethyl-α-alkanol are added to the trithio intermediate mixtureand reacted in the presence of additional base, see V, VI, and VII. Theformed reaction product, see IX, is subsequently acidified, thuscompleting the reaction and forming the above describeds,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compound,see X.

The reaction is carried out at a temperature sufficient to complete theinteraction of the reactants so as to produce thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundin a desired time. The reaction can be carried out at any temperaturewithin a wide range from about the freezing point of the reaction massto about the reflux temperature of the solvent. The reaction temperatureis generally from about minus 15° C. to about 80° C., desirably fromabout 0° C. to about 50° C., and preferably from about 15° C. to about35° C., with room temperature being preferred. The reaction can beperformed at atmospheric pressure. The reaction time depends uponseveral factors, with the temperature being most influential. Thereaction is generally complete within 20 hours and preferably within 10hours.

A phase transfer catalyst is preferably utilized if a solvent is used inthe reaction. Examples of solvents are set forth herein below. Theketone utilized in the reaction may double as a solvent, and thereforeno catalyst usually is needed. The amount of phase transfer catalyst,when utilized in the present invention, is generally from about 0.1 molepercent to about 10 mole percent, desirably from about 0.5 mole percentto about 5 mole percent and preferably from about 2 mole percent toabout 4 mole percent per mole of carbon disulfide. The phase transfercatalysts can be polyether, and/or an onium salt including a quaternaryor tertiary organic compound of a group VA or VIA element of thePeriodic Table and salts thereof. Most preferred are quaternary amines,and salts thereof.

”Onium salts“ more particularly refer to tertiary or quaternary aminesand salts such as are generally used in the phase transfer catalysis ofheterogeneous reaction in immiscible liquids. The general requirementfor the onium salt chosen is that it be soluble in both the organic andaqueous phases, when these two liquid phases are present, and usually alittle more soluble in the organic phase than the aqueous phase. Thereaction will also proceed with a phase transfer catalyst when there isonly a single organic liquid phase present, but such a reaction is lesspreferable than one in which both aqueous and organic liquid phases arepresent. A wide variety of onium salts is effective in this ketoformsynthesis.

The onium salts include the well-known salts, tertiary amines andquaternary compounds of group VA elements of the Periodic Table, andsome Group VIA elements such as are disclosed in the U.S. Pat. No.3,992,432 and in a review in Angewandte Chemie, International Edition inEnglish, 16 493-558 (August 1977). Discussed therein are various aniontransfer reactions where the phase transfer catalyst exchanges itsoriginal ion for other ions in the aqueous phase, making it possible tocarry our chemistry there with the transported anion, including OH-ions.

The onium salts used in this synthesis include one or more groups havingthe formula (R_(n)Y)⁺X⁻, wherein Y is either a pentavalent ion derivedfrom an element of Group VA, or a tetravalent ion derived from anelement of Group VIA; R is an organic moiety of the salt molecule bondedto Y by four covalent linkages when Y is pentavalent, and three covalentlinkages when Y is tetravalent; X⁻ is an anion which will dissociatefrom the cation (R_(n)Y)⁺ in an aqueous environment. The group(R_(n)Y)⁺X⁻ may be repeated as in the case of dibasic quaternary saltshaving two pentavalent Group VA ions substituted in the mannerdescribed.

The preferred onium salts for use in the invention have the formula(R^(A)R^(B)R^(C)R^(D)Y⁺)X⁻wherein Y is N or P, and R¹-R⁴ are monovalent hydrocarbon radicalspreferably selected from the group consisting of alkyl, alkenyl, aryl,alkaryl, aralkyl, and cycloalkyl moieties or radicals, optionallysubstituted with suitable heteroatom-containing functional groups. Theonium salts are generally selected to be less preferentially lesssoluble in the less polar of the two distinct liquid phases. Any of thesalts disclosed in the U.S. Pat. No. 3,992,432 will be found effective,but most preferred are those in which the total number of carbon atomsin R^(A), R^(B), R^(C), and R^(D) cumulatively range from about 13 toabout 57, and preferably range from about 16 to about 30. Most preferredonium salts have Y═N, and hydrocarbon radicals where R^(A) is CH₃, andR^(B), R^(C), and R^(D) are each selected from the group consisting ofn-C₂H₅, n-C₄H₅; n-C₅H₁₁; mixed C₅H₁₇; n-C₁₂H₂₅; n-C₁₈H₃₇; mixed C₈-C₁₀alkyl; and the like. However, R^(A) may also be selected from C₂H₅n-C₃H₇and n-C₄H₉ benzyl.

Various counterions may be used, including Cl⁻, Br⁻, I⁻, NO₃ ⁻, SO₄ ⁻²,HSO₄ ⁻ and CH₂CO₂ ⁻. Most preferred is Cl⁻.

The tertiary amines or triamines useful as phase transfer catalysts inthis synthesis include the alkyl amines and the aryldialkylamines,exemplified by tributylamine and phenyldibutylamine respectively, whichare commonly available, wherein each alkyl may have from 1 to about 16carbon atoms.

The polyethers useful as catalysts in this synthesis include cyclicpolyethers such as the crown ethers, disclosed in Agenwandte Chemie,supra, and acyclic polyethers having the formulaR—O—R^(E)wherein R and R^(E) are, independently, alkyls having from 1 to about 16carbon atoms, or alkyl containing substituted functional groups such ashydroxy, sulfur, amine, ether, etc. Most preferred acyclic polyethershave the formulaR—(OCH₂CH₂), OR″wherein

-   -   R is an alkyl having from 1 to about 16 carbon atoms    -   R″ is an alkyl having from 1 to about 16 carbon atoms, or H, and    -   r is an integer in the range from 0 to about 300.        Most preferred are commonly available polyethers such as:        tetraethylene glycol dimethyl ether; polyethylene oxide (mol wt.        About 5000); poly(ethylene glycol methyl ether);        1,2-dimethoxyethane; diethyl ether, and the like.

Polyether catalysts are especially desirable in this ketoform synthesisbecause they are directive so as to produce a preponderance of thedesired symmetrically substituted isomer, in a reaction which isremarkably free of undesirable byproducts, which reaction proceeds witha relatively mild exotherm so that the reaction is controllable.

The organic solvent may be any solvent in which the reactants aresoluble and include hydrohalomethylenes, particularlyhydrochloromethylenes, sulfolane, dibutyl ether, dimethyl sulfone,diisopropyl ether, di-n-propyl ether, 1,4-dioxane, tetrahydrofuran,benzene, toluene, hexane, carbon tetrachloride, heptane, mineral spiritsand the like. Most preferred solvents are heptanes and mineral spirits.Solvent is generally utilized in an amount generally from about 10 toabout 500 percent and preferably from about 50 percent to about 200percent based on the total weight of the reactants.

Insofar as the reactive components are concerned, any of various ketoneshaving the general formula:

can be employed in the synthesis, wherein R¹ and R² are described hereinabove. As carbon disulfide is the controlling agent in the reaction, theketone is generally used in an amount from about 110 mole percent toabout 2,000 mole percent per mole of carbon disulfide. When the ketoneis used as a solvent, it is generally utilized in an amount of fromabout 150 mole percent to about 300 mole percent, and preferably fromabout 180 mole percent to about 250 mole percent per mole of carbondisulfide.

The alkali bases suitable for use in the synthesis of the presentinvention include, but are not limited to, sodium hydroxide andpotassium hydroxide. The base is utilized in an amount generally fromabout 5 times to about 15 times the number of moles of carbon disulfideand preferably from about 6 to about 10 times the number of moles ofcarbon disulfide utilized in the reaction.

The acids used in the acidification step include, but are not limitedto, hydrochloric acid, sulfuric acid, phosphoric acid, etc. The acidsare utilized in amounts suitable to make the aqueous solution acidic.

The haloform of the present invention has the general formula CHX₃wherein X is, independently, chlorine or bromine. The amount of haloformused in the present invention is generally from about 110 mole percentto about 2000 mole percent, desirably from about 150 mole percent toabout 300 mole percent, and preferably 180 mole percent to about 250mole percent per mole of carbon disulfide. Examples of haloformsinclude, but are not limited to, chloroform and bromoform, andchloroform is the preferred haloform of the present invention.

Alternatively, instead of adding both a haloform and a ketone, to thereaction mixture, an α-trihalomethyl-α-alkanol can be substitutedtherefore. The amount of α-trihalomethyl-α-alkanol utilized in thereaction generally is from about 110 mole percent to about 2000 molepercent, desirably is from about 150 mole percent to about 300 molepercent, and preferably is from about 180 mole percent to about 250 molepercent per mole of carbon disulfide. The general formula of theα-trihalomethyl-α-alkanol is generally represented as follows:

wherein X, R¹ and R² are defined above.

While not wishing to be limited to any particular mechanism, it isbelieved that the specific mechanism for the reaction process is asfollows:

Initially, the carbon disulfide and sodium hydroxide are reacted.

In the subsequent step of the reaction, the chloroform is reacted withthe ketone as follows:

Then, the following is reacted:

The overall reaction is as follows:

The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompounds produced by the present invention can generally be classifiedas inifertors, meaning that they act as both a chain transfer agent andan initiator. The use of other types of inifertors for block copolymerswas discussed by Yagei and Schnabel in Progress in Polymer Science 15,551 (1990) and is hereby fully incorporated by reference.

Thus, the compounds of the present invention can be utilized asinitiators to initiate or start the polymerization of a monomer. Theycan also act as a chain transfer agent, which interrupts and terminatesthe growth of a polymer chain by formation of a new radical which canact as a nucleus for forming a new polymer chain. The compounds can alsobe utilized as terminators in that when most of initiating radicals andmonomers are consumed, the compounds are incorporated in the polymers asa dormant species. Desirably though, another compound, such as thoselisted herein below, is often used as an initiator in the free radicalpolymerization process as described herein below, and thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention will act as a chain-transfer agent.

The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompounds of the present invention can be used as chain transfer agentsin a free radical polymerization process to provide polymerizationswhich have living characteristics and polymers of controlled molecularweight and low polydispersity, as well as for forming telechelicpolymers.

A living polymerization is a chain polymerization which proceeds in theabsence of termination and chain transfer. The following experimentalcriteria can be utilized to diagnose a living polymerization.

-   1. Polymerization proceeds until all monomer has been consumed.    Further addition of monomer results in continued polymerization.-   2. The number average molecular weight, M_(n) (or X_(n), the number    average degree of polymerization), is a linear function of    conversion.-   3. The number of polymer molecules (and active centres) is constant    and independent of conversion.-   4. The molecular weight can be controlled by the stoichiometry of    the reaction.-   5. Narrow molecular weight distribution polymers are produced.-   6. Chain-end functionalized polymers can be prepared in quantitative    yields.-   7. In radical polymerization, the number of active end groups should    be 2, one for each end.

Besides those mentioned above, other criteria can also help to determinethe living character of polymerization. For radical livingpolymerization, one is the ability of the polymer isolated from thefirst step of polymerization to be used as a macroinitiator for thesecond step of a polymerization in which block copolymers or graftedpolymers are ultimately formed. To confirm the formation of blockcopolymers, measurements of molecular weights and a determination of thestructure of the blocks are employed. For structure measurements, theexamination of NMR or IR signals for the segments where individualblocks are linked together and a determination of the end groups areboth very important. In radical polymerization, only some of thecriteria for living polymerizations are actually fulfilled. Due to theirability to undergo further polymerization, these types of polymers canalso be called ‘reactive polymers’. A more detailed description ofliving polymerization can be found in ”Living Free-Radical BlockCopolymerization Using Thio-Inifertors“, by Anton Sebenik, Progress inPolymer Science, vol. 23, p. 876, 1998.

The living polymerization processes can be used to produce polymers ofnarrow molecular weight distribution containing one or more monomerssequences whose length and composition are controlled by thestoichiometery of the reaction and degree of conversion. Homopolymers,random copolymers or block polymers can be produced with a high degreeof control and with low polydispersity. Low polydispersity polymers arethose with polydispersities that are significantly less than thoseproduced by conventional free radical polymerization. In conventionalfree radical polymerization, polydispersities (polydispersity is definedas the ratio of the weight average to the number average molecularweight M_(w)/M_(n)) of the polymers formed are typically greater than2.0. Polydispersities obtained by utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsand derivatives thereof of the present invention are preferably 1.75 or1.5, or less, often 1.3 or less, and, with appropriate choice of thechain transfer agent and the reaction conditions, can be 1.25 or less.

When the s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatescompounds are utilized only as chain-transfer agents, the polymerizationcan be initiated with other initiators at lower temperature whileyielding polymers with similarly controlled fashion.

Free radical polymerizations utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsas both initiators and chain transfer agents generally form telechelicpolymers. When an initiator other than thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundis also utilized, a polymer having a single functional end group isformed in proportion to the amount of said other initiator to thiss,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundutilized.

The free radical living polymerization process of the invention can beapplied to any monomers or monomer combinations which can befree-radically polymerized. Such monomers include one or more conjugateddiene monomers or one or more and vinyl containing monomers, orcombinations thereof.

The diene monomers have a total of from 4 to 12 carbon atoms andexamples include, but are not limited to, 1,3-butadine, isoprene,1,3-pentadiene, 2,3-dimethyl-1-3-butadeine, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, and combinations thereof.

The vinyl containing monomers have the following structure:

where R³ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR⁵), carboxy, acyloxy, aroyloxy(O₂CR⁵),alkoxy-carbonyl(CO₂R⁵), or aryloxy-carbonyl; and R⁴ comprises hydrogen,R⁵, CO₂H, CO₂R⁵, COR⁵, CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵, or halogen. R⁵comprises C₁ to C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituentsindependently comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- oraryloxy-carbonyl, isocyanato, cyano, silyl, halo and dialkylamino.Optionally, the monomers comprise maleic anhydride, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers.Monomers CH₂═CR³R⁴ as used herein include C₁-C₈ acrylates andmethacrylates, acrylate and methacrylate esters, acrylic and methacrylicacid, styrene, α methyl styrene, C₁-C₁₂ alkyl styrenes with substitutegroups both either on the chain or on the ring, acrylamide,methacrylamide, and methacrylonitrile, mixtures of these monomers, andmixtures of these monomers with other monomers. As one skilled in theart would recognize, the choice of comonomers is determined by theirsteric and electronic properties. The factors which determinecopolymerizability of various monomers are well documented in the art.For example, see: Greenley, R. Z., in Polymer Handbook, 3^(rd) Edition(Brandup, J., and Immergut, E. H. Eds.) Wiley: N.Y., 1989 pII/53.

Specific monomers or comonomers include the following: methylmethacrylate, ethyl methacrylate, propyl methacrylate (all isomers),butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornylmethacrylate, methacrylic acid, benzyl methacrylate, phenylmethacrylate, methacrylonitrile, alpha-methylstyrene. methyl acrylate,ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (allisomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid,benzyl acrylate, phenyl acrylate, acrylonitrile. styrene, functionalmethacrylates, acrylates and styrenes selected from glycidylmethacrylate, 2-hydroxyethyl, methacryliate, hydroxypropyl methacrylate(all isomers), hydroxybutyl methacrylate (all isomers),N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate,triethyleneglycol methacrylate, itaconic anhydride, itaconic acid,glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrviate (allisomers), hydroxybutyl acrylate (all isomers), N,N-dimethylaminoethylacrylate, N,N-diethylaminoethyl acrylate, triethyleneglycol acrylate,methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide,N-terbtbutylmethacrylamide, N-n-butylmethacrylamide,N-methylolmethacrylamide, N-ethylotmethacrylamide.N-tert-butylacrylamide. N-n-butylacrylamide, N-methylolacrylamide,N-ethylolacrylamide, vinyl benzoic acid (all isomers),dethylaminostyrene (all isomers), alpha-methylvinyl benzoic acid (allisomers), dethylamino alpha-methylstyrene (all isomers). p-vinylbenzenesulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilyipropyl methacrylate, dimethoxymethylsilylpropylmethacrylate, diethoxymethylslylpropyl methacrylate, dibutoxymethylsilypropyl methacrylate, d iisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy, silylpropyl methacrylate,diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate,triethoxysifylylpropyl acrylate, tributoxysilylpropyl acrylate,dimethoxymethylsilylpropyl acrylate, d iethoxymethylsilylpropylacrylate, d ibutoxymethylsilylpropyl acrylate,diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate,diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene, and combinations thereof.

Preferred monomers are C₁-C₈ acrylates, C₁-C₈ methacrylates, styrene,butadiene, isoprene and acrylonitrile.

As noted above, in order to initiate the free radical polymerizationprocess, it is often desirable to utilize an initiator as a source forinitiating free radicals Generally, the source of initiating radicalscan be any suitable method of generating free radicals such as thethermally induced homolytic scission of a suitable compound(s) (thermalinitiators such as peroxides, peroxyesters, or azo compounds), thespontaneous generation from monomer (e.g., styrene), redox initiatingsystems, photochemical initiating systems or high energy radiation suchas electron beam, X- or gamma-radiation. The initiating system is chosensuch that under the reaction conditions there is no substantial adverseinteraction of the initiator or the initiating radicals with thetransfer agent under the conditions of the experiment. The initiatorshould also have the requisite solubility in the reaction medium ormonomer mixture. The s,s′-bis-(α,α′-disubstituted-α′-aceticacid)-trithiocarbonate compounds of the invention can serve as aninitiator, but the reaction must be run at a higher temperature.Therefore, optionally it is desirable to utilize an initiator other thanthe s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatescompounds of the present invention.

Thermal initiators are chosen to have an appropriate half-life at thetemperature of polymerization. These initiators can include one or moreof the following compounds:

2,2′-azobis(isobutyronitrile)(AIBN), 2,2′-azobis(2-cyano-2-butane),dimethyl 2,2′-azobisdimethylisobutyrate, 4,4′-azobis(4-cyanopentanoicacid), 1,1′-azobis(cyclohexanecarbanitrile),2-(t-butylazo)-2-cyanopropane,2,2′-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide,2,2′-azobis[2-methyl-N-hydroxyethyl)]-propionamide,2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride,2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′-azobis(N,N′-dimethyleneisobutyramine),2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide),2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide),2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],2,2′-azobis(isobutyramide) dehydrate,2,2′-azobis(2,2,4-trimethylpentane), 2,2′-azobis(2-methylpropane),t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate,t-butylperoxyneodecanoate, t-butylperoxy isobutyrate, t-amylperoxypivalate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate,dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide,dilauroylperoxide, potassium peroxydisulfate, ammonium peroxydisulfate,di-t-butyl hyponitrite, dicumyl hyponitrite.

Photochemical initiator systems are chosen to have the requisitesolubility in the reaction medium or monomer mixture and have anappropriate quantum yield for radical production under the conditions ofthe polymerization. Examples include benzoin derivatives, benzophenone,acyl phosphine oxides, and photo-redox systems production under theconditions of the polymerization; these initiating systems can includecombinations of the following oxidants and reductants:

-   -   oxidants: potassium peroxydisuffate, hydrogen peroxide, t-butyl        hydroperoxide reductants: iron (11), titanium (111), potassium        thiosulfite, potassium bisulfite.

Other suitable initiating systems are described in recent texts. See,for example, Moad and Solomon ”The Chemistry of Free RadicalPolymerization“. Pergamon, London. 1995. pp 53-95.

The preferred initiators of the present invention are2,2′-azobis(isobutyronitrile)(AIBN), or 4,4′-azobis(4-cyanopentanoicacid), or 2,2′-azobis(2-cyano-2-butane), or1,1′-azobis(cyclohexanecarbanitrile). The amount of initiators utilizedin the polymerization process can vary widely as generally from about0.001 percent to about 99 percent, and desirably from about 0.01 percentto about 50 or 75 percent based on the total moles of chain transferagent utilized. Preferably small amounts are utilized from about 0.1percent to about 5, 10, 15, 20, or 25 mole percent based on the totalmoles of chain transfer agent utilized, i.e. saids,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compounds.In order to form polymers which are predominately telechelic, initiatorsother than the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds are utilized in lesser amounts, such asfrom about 0.001 percent to about 5 percent, desirably from about 0.01percent to about 4.5 percent, and preferably from about 0.1 percent toabout 3 percent based on the molar equivalent to the total moles ofchain transfer agent utilized.

Optionally, as noted above, solvents may be utilized in the free radicalpolymerization process. Examples of such solvents include, but are notlimited to, C₆-C₁₂ alkanes, toluene, chlorobenzene, acetone, t-butylalcohol, and dimethylformamide. The solvents are chosen so that they donot chain transfer themselves. The amount of solvent utilized in thepresent invention polymerization process is generally from about 10percent to about 500 percent the weight of the monomer, and preferablyfrom about 50 percent to about 200 percent the weight of the monomerutilized in the polymerization.

As stated above, it is preferable to utilize thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the invention as chain transfer agents in the free radicalpolymerization process. The amount of chain transfer agent (CTA)utilized depends on the desired molecular weight of the polymer to beformed and can be calculated as known by one skilled in the art. Aformula for calculating the amount of chain transfer agent is asfollows:

${{Mn}\mspace{14mu}{of}\mspace{14mu}{polymer}} = \left( \frac{\begin{matrix}{{Weight}\mspace{14mu}{of}\mspace{14mu}{monomer} \times} \\{{{molecular}\mspace{14mu}{weight}{\mspace{11mu}\;}C\; T\; A} +} \\{{molecular}\mspace{14mu}{weight}\mspace{14mu}{of}\mspace{14mu} C\; T\; A}\end{matrix}}{{Weight}\mspace{14mu}{of}\mspace{14mu} C\; T\; A} \right)$

While not wishing to be limited to any particular mechanism, it isbelieved that the mechanism of the free radical living polymerizationprocess is as follows when using a vinyl monomer:

Alternatively, the reaction can proceed as follows:

As can be seen from the above mechanism, polymers having two differentstructures, see XIX and XXII, can be formed. The resulting polymers areeither telechelic polymers (formed by the trithiocarbonate compounds ofthe present invention) with identical functional groups at the ends ofthe chain, or a polymer having a single functional end group and also aninitiator terminated chain (formed by using a conventional initiatorsuch as AIBN). As stated above, the ratios between the resultingpolymers can be controlled to give desired results and generally dependson the amount of initiator utilized. Obviously, if the initiator is theonly s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompound of the present invention, the resulting polymers are alwaystelechelic. The greater the amount of the other initiator utilized,proportionally decreases the amount of telechelic polymers formed.Generally, the amount of the repeat group m, m′, m″, n, n′, or n″, isgenerally from about 1 to about 10,000, desirably from about 5 to about500, and preferably from about 10 to about 200. Inasmuch as one or morevinyl monomers and/or one or more diene monomers can be utilized, it isto be understood that repeat groups of the polymers of the presentinvention are generally indicated by formulas XIX and XXII and can bethe same or different. That is, random copolymers, terpolymers, etc.,can be formed within either of the two repeat groups noted, as well asblock copolymers which can be formed by initially adding one monomer andthen subsequently adding a different monomer (e.g. an internal blockcopolymer).

The polymers formed by the present invention can be generallyrepresented by the following formula:

wherein such monomers are described herein above. Of course, the aboveformula can contain an initiator end group thereon as in XXII.

The reaction conditions are chosen as known to one skilled in the art sothat the temperature utilized will generate a radical in a controlledfashion, wherein the temperature is generally from about roomtemperature to about 200° C. The reaction can be run at temperatureslower than room temperature, but it is impractical to do so. Thetemperature often depends on the initiator chosen for the reaction, forexample, when AIBN is utilized, the temperature generally is from about40° C. to about 80° C., when azo dicyanodivaleric acid is utilized, thetemperature generally is from about 50° C. to about 90° C., whendi-t-butylperoxide is utilized, the temperature generally is from about110° C. to about 160° C., when s,s′-bis-(α,α′-disubstituted-α″-aceticacid) is utilized, the temperature is generally from about 80° C. toabout 200° C.

The low polydispersity polymers prepared as stated above by the freeradical polymerization can contain reactive end groups from the monomerswhich are able to undergo further chemical transformation or reactionsuch as being joined with another polymer chain, such as to form blockcopolymers for example. Therefore, any of the above listed monomers,i.e. conjugated dienes or vinyl containing monomers, can be utilized toform block copolymers utilizing the s,s′-bis-(α,α′-distributed-α″-aceticacid)-trithiocarbonate compounds as chain transfer agent. Alternatively,the substituents may be non-reactive such as alkoxy, alkyl, or aryl.Reactive groups should be chosen such that there is no adverse reactionwith the chain transfer agents under the conditions of the experiment.

The process of this invention can be carried out in emulsion, solutionor suspension in either a batch, semi-batch, continuous, or feed mode.Otherwise-conventional procedures can be used to produce narrowpolydispersity polymers. For lowest polydispersity polymers, the chaintransfer agent is added before polymerization is commenced. For example,when carried out in batch mode in solution, the reactor is typicallycharged with chain transfer agent and monomer or medium plus monomer.The desired amount of initiator is then added to the mixture and themixture is heated for a time which is dictated by the desired conversionand molecular weight. Polymers with broad, yet controlled,polydispersity or with multimodal molecular weight distribution can beproduced by controlled addition of the chain transfer agent over thecourse of the polymerization process.

In the case of emulsion or suspension polymerization the medium willoften be predominately water and the conventional stabilizers,dispersants and other additives can be present. For solutionpolymerization, the reaction medium can be chosen from a wide range ofmedia to suit the monomer(s) being used.

As already stated, the use of feed polymerization conditions allows theuse of chain transfer agents with lower transfer constants and allowsthe synthesis of block polymers that are not readily achieved usingbatch polymerization processes. If the polymerization is carried out asa feed system the reaction can be carried out as follows. The reactor ischarged with the chosen medium, the chain transfer agent and optionallya portion of the monomer(s). The remaining monomer(s) is placed into aseparate vessel. Initiator is dissolved or suspended in the reactionmedium in another separate vessel. The medium in the reactor is heatedand stirred while the monomer+medium and initiator+medium are introducedover time, for example by a syringe pump or other pumping device. Therate and duration of feed is determined largely by the quantity ofsolution the desired monomer/chain transfer agent/initiator ratio andthe rate of the polymerization. When the feed is complete, heating canbe continued for an additional period.

Following completion of the polymerization, the polymer can be isolatedby stripping off the medium and unreacted monomer(s) or by precipitationwith a non-solvent. Alternatively, the polymer solution/emulsion can beused as such, if appropriate to its application.

The invention has wide applicability in the field of free radicalpolymerization and can be used to produce polymers and compositions forcoatings, including clear coats and base coat finishes for paints forautomobiles and other vehicles or maintenance finished for a widevariety of substrates. Such coatings can further include pigments,durability agents, corrosion and oxidation inhibitors, rheology controlagents, metallic flakes and other additives. Block and star, andbranched polymers can be used as compatibilisers, thermoplasticelastomers, dispersing agents or rheology control agents. Additionalapplications for polymers of the invention are in the fields of imaging,electronics (e.g., photoresists), engineering plastics, adhesives,sealants, and polymers in general.

As can be seen in the above shown polymerization mechanism, thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundcan be utilized to create telechelic polymers having two functionalgroups at both chain ends.

The term ”telechelic polymer“ was proposed in 1960 by Uraneck et al. todesignate relatively low molecular weight macromolecules possessing oneor more, and preferably two reactive functional groups, situated at thechain ends, thereof. The functional end groups of both thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundand the polymers formed therefrom, have the capacity for selectivereaction to form bonds with another molecule. The functionality of atelechelic polymer or prepolymer is equal to the number of such endgroups. Telechelic polymers containing a functional group, such as COOH,at each end are useful for synthesizing further chain extendedcopolymers and block copolymers.

The interest in telechelic polymers resides in the fact that suchpolymers can be used, generally together with suitable linking agents,to carry out three important operations: (1) chain extension of shortchains to long ones by means of bifunctional linking agents, (2)formation of networks by use of multifunctional linking agents, and (3)formation of (poly)block copolymers by combination of telechelics withdifferent backbones. These concepts are of great industrial importancesince they form the basis of the so-called ”liquid polymer“ technologyexemplified by the ”reaction injection molding“ (RIM). Great interesthas also been shown by the rubber industry because the formation of arubber is based on network formation. In classical rubber technology,this is achieved by the cross-linking of long chains that show highviscosity. The classical rubber technology, therefore, requires anenergy-intensive mixing operation. The use of liquid precursors, whichcan be end-linked to the desired network, offers not only processingadvantages, but in some cases, also better properties of theend-product. Further information about telechelic polymers and synthesisthereof can be found in ”Telechelic Polymers: Synthesis andApplications“ by Eric J. Goethe, CRC Press, Boca Raton, Fla., 1989.

The reaction conditions for the reactive functional acid end groups ofthe telechelic polymers or s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds of the present invention are generallythe same as those for forming the above noted free radical polymers. Theacid in the monomeric or in the polymeric form can be transformed to itsderivatives in the conventional manner. For example, the ester can bemade by refluxing the acid in alcohol with an acid catalyst with removalof water. Amides can be formed by heating the acid with an amine withthe removal of water. 2-hydroxy-ethyl ester can be formed by directlyreacting the acid with an epoxide with or without a catalyst such astriphenylphosphine or an acid like toluene-sulfonic acid. As seen by theexamples below, any of the above noted monomers such as the one or morediene monomers or one or more vinyl containing monomers, can be utilizedto form the telechelic monomers from the bis-(α,α′-distributed-α″-aceticacid)-trithiocarbonate compounds of the present invention. Any of theabove noted components, such as solvent, etc., can be utilized in theherein above stated amounts.

The acid groups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound can be converted to other functionalgroups either before or after polymerization. Even if thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundshave functional end groups which have been converted from the acid endgroups before polymerization, the monomers added during polymerizationstill add to the chain between the sulfur-tertiary carbon as shown inthe mechanisms above as well as below at XXIII and XXIV. The carboxylicend groups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds or the polymerizeds,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundscan be converted or changed into other functional end groups such asesters, thioesters, amides, beta mercapto esters, beta hydroxy esters,or beta amino esters. Examples of these functional end groups are shownbelow.

An example reaction forming a telechelic polymer from thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the invention when using a vinyl monomer is as follows:

Of course, it is to be understood as indicated above, that the repeatunits m and n can be derived either from conjugated diene monomers, orthe indicated vinyl monomers, or combinations thereof, as generally setforth in formula W.

Subsequently, other functional end groups can be derived from the acidgroups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound and can generally be represented by theformula:

where E is set forth below. For example,

wherein E is XR′, that is R′, independently, comprises H, C₁-C₁₈ alkylswhich can be optionally substituted with one or more halogen, hydroxyl,or alkoxy, C₁-C₁₈ hydroxyalkyls, and C₁-C₁₈ aminoalkyls and X comprisesoxygen, sulfur, NH, or NR′.

The following is still another example of functional end groups whichcan be derived from the acid:

wherein E is

that is where R⁶ through R⁹, independently comprise H, C₁-C₁₈ alkyls,aryl groups or substituted aryl groups having from 1 to 6 substituentson the ring, such as halogen, hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkys,C₁-C₁₈ aminoalkyls, C₁-C₁₈ mercapto alkyls, and the like. Y can compriseoxygen, sulfur, NH, or NR⁶ to R⁹.

A further example of still other functional end groups which can bederived from the acid groups of thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsis as follows:

wherein E is OR¹⁰, that is where Z can comprise a leaving group, such asa halide or alkylsulfonate or aryl sulfonate. R¹⁰ can comprise C₁-C₁₈, aalkyl or substituted alkyl wherein said substituent is halogen,hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkyl or C₁-C₁₈ amino alkyl and thelike.

Preparation of the above shown methylesters ofs,s′-bis-(2-methyl-2-propanoic acid)-trithiocarbonate is as follows:s,s′-bis-(2-methyl-2-propanoic acid) trithiocarbonate (R¹, R²═CH³) (2.82g, 0.01 mole), Sodium carbonate powders (3.18 g, 0.03 mole) and 15 mldimethyl formamide were stirred under nitrogen at 40° C. while asolution of methyliodide (3.41 g, 0.024 mole) in 2 ml dimethylformamidewas added dropwise over 10 minutes. The reaction was stirred at 40-50°C. for 2 hours, poured into 25 ml H₂O and extracted 3 times with a totalof 200 ml. ether. The etherate solution was dried over magnesium sulfateand concentrated. The yellow solid was further purified byrecrystallization from hexanes. Infrared and H′NMR showed the abovedesired product.

An example of an already formed telechelic polymer, made from a vinylmonomer, undergoing conversion of the acid end group is as follows:

where m and n are as set forth above.

The above structure (XXXIV) was formed by reaction of epoxide withs,s′-bis-(2-methyl-2-propanoic acid)-trithiocarbonate (I)(R¹, R²═CH₃,0.01 mole) of the present invention and Epon® Resin 828 (Shellchemicals, reaction product of bisphenol A and epichlorohydrin, 80-85%diglycidyl ethers of bisphenol A) (70 g) and trephenyl phosphine (0.12g) were heated to 95° C. under nitrogen. The reaction was monitored forthe disappearance of the carboxylic acid by titration. It was found thereaction was essentially complete in 1.5 hours. The product structurecan be further confirmed by mass spectroscopy.

Another aspect of present invention further relates to forming thefollowing compounds:

wherein R¹¹ comprises a benzyl group, C₁-C₁₈ alkyl, or substituted alkylsuch as halogen, hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkyl,carboxylalkyl, or carboalkoxyalkyl. Q⁺X is a phase transfer catalystsuch as tetrabutylammoniumhydrogensulfate, oroctadecyltrimethylammoniumchloride (Aliquot 336).

The resulting compound is an s-substitutedalkyl-s′-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate. R¹¹ is analkyl having from 1-18 carbon atoms, aralkyl, hydroxyalkyl, cyanoalkyl,aminoalkyl, carboxylalkyl, or carboalkoxyalkyl, mercaptoalkyl, etc. R¹and R² are as stated herein above.

When s-substituted alkyl-s′-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate is employed either as an inifertor, or as achain-transfer agent, unless R¹¹ is carboxyl alkyl, only one end of thepolymer has a carboxyl function, i.e. it is no longer a telechelicpolymer.

While various polymers have been set forth herein above, it is to beunderstood that any of the carboxyl terminated polymers, such as W, orthe E terminated polymers, and the like, can be reacted with one or moremonomers and/or one or more polymers know to the art and to theliterature to yield various resulting block polymers which are derivedfrom the same monomer or from two or more different monomers. Forexample, each acid end group can be reacted with an excess of an epoxycompound such as a glycidyl bisphenol A and then subsequentlypolymerized with additional glycidyl bisphenol A to form an epoxypolymer. Naturally, other block polymers or copolymers can be reactedwith the carboxylic end group or the other end groups generally denotedby E herein above.

The present invention will be better understood by reference to thefollowing examples which serve to describe, but not to limit, thepresent invention.

EXAMPLES Example 1 Synthesis of s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate, (R¹═R²═CH₃)

Procedure:

In a 500 ml jacketed flask equipped with a mechanical stirrer, athermometer, a reflux condenser and an addition funnel added 22.9 gramsof carbon disulfide, 2.0 gram of tetrabutylammonium bisulfate and 100 mltoluene. The solution was stirred at 20° C. under nitrogen and 168 gramsof 50% sodium hydroxide solution was added dropwise to keep thetemperature between 20-30° C. 30 min. after the addition, a solution of43.6 grams of acetone and 89.6 grams of chloroform was added at 20-30°C. The reaction was then stirred at 15-20° C. overnight. 500 ml waterwas added to the mixture, the layers were separated. The organic layerwas discarded and the aqueous layer was acidified with concentrated HClto precipitate the product as yellow solid. 50 ml toluene was added tostir with the mixture. Filtered and rinsed the solid with toluene tocollect 22.5 grams of product after drying in the air to constantweight.

Example 2 Synthesis of s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates. (R¹═R²═CH₃)

The procedure was essentially the same as in example 1, except thatmineral spirits replaced toluene as solvent. 40.3 grams of product wasobtained as yellow solid.

Example 3 Synthesis of s-alkyl-s-(-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates

Procedure:

Dodecylmercaptan (0.1 mole), and Aliquot 336 (0.004 mole) was dissolvedin 48 g acetone. 50% sodium hydroxide solution (0.105 mole) was added,followed by dropwise addition of carbon disulfide (0-1 mole) in 10 gacetone solution. The media turned from colorless to yellow. After 20min., chloroform (0.15 mole) was added followed by dropwise addition of50% NaOH (0.5 mole) and 5 g NaOH beads. The r×n was stirred at 15-20° C.overnight, filtered and the sol. was rinsed with acetone. The acetonelayer was concentrated to dryness. The mass was dissolved in water,acidified with concentrated HCl to precipitate the product, rinsed withwater to collect the yellow solid. The solid was dissolved in 350 mlhexanes. The solution was dried over magnesium sulfate and filtered. Theorganic solution was cooled to precipitate the product as yellow flakes.Yield is 85%.

Example 4 Polymerization of Prior Art Compounds

Procedure:

Dibenzyltrithiocarbonate (1.54 g, 5.3 mmole), 2-ethylhexylacrylate (25grams 135.7 mmole), AIBN (0.05 g, 0.3 mmole) and acetone (25 ml) weremixed. 1 ml of undecane was added as GC internal standard forcalculating the conversion. The solution was purged with nitrogen for 15min. before heating to 52° C. under nitrogen. No exotherm was detectedthroughout the reaction. Aliquots of the sample were taken for GC andGPA analyses during the course of the polymerization. The followingtable showed the progress of the polymerization in 7 hours.

Sample Time (mins.) Mn Mw Conv. % 1 2 120 866 970 3.7 3 270 1180 142813.2 4 420 1614 2059 26.9

Example 5 Polymerization with s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates

Procedure:

Following the same procedure as in example 4, the novel tricarbonate(1.50 g, 5.3 mmole), 2-ethylhexylacrylate (25 g, 135.7 mmole), AIBN(0.05 g, 0.3 mmole) and acetone (25 ml) were mixed. 1 ml of undecane wasadded as internal standard The reaction was stirred at 52° C. for 7hours. The following table showed the conversion and the molecularweights of the resulting polymer.

Sample Time (mins.) Mn Mw Conv. % 1 45 669 724 3.5 2 120 1433 1590 25.83 240 3095 3621 79.8 4 300 3345 3898 87.9 5 420 3527 4136 93.9

Example 6 Polymerization with s,s′-bis-(α,α′-disubstituted-α″-aceticacid) trithiocarbonates

Procedure:

This is a bulk polymerization with the trithiocarbonate aschain-transfer agent The trithiocarbonate (1.0 g, 3.5 mmole),2-ethylhexylacrylate (25 g, 135.7 mmole), AIBN (0.05 g, 0.3 mmole) and 1ml undecane (internal standard) were purged with nitrogen, then heatedto 60° C. for 3 hours. The following table showed the conversion and themolecular weight of the polymer.

Sample Time (mins.) Mn Mw Conv. % 1 30 2229 2616 35.6 2 90 4501 552691.9 3 180 4672 5780 97.8

Example 7 Polymerization with s,s′-bis-(α,α′-disubstituted-α′-aceticacid) trithiocarbonates

Procedure:

The trithiocarbonate was used as inifertor. Trithiocarbonate (1.0 g, 3.5mmole), n-butylacrylate (20 g, 156.1 mmole) with 1 ml decane as internalstandard were purged with nitrogen for 15 min., then polymerized at 130°C. under nitrogen for 6 hours. The following table showed the conversionand the molecular weights of the polymer.

Sample Time (mins.) Mn Mw Conv. % 1 60 1118 1242 16.0 2 120 1891 219932.5 3 240 2985 3337 52.5 4 360 3532 4066 65.7

Example 8 Free Radical Polymerization Utilizings,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates asinfifertor

Procedure:

The trithiocarbonate (2.0 g, 7.1 mmole) and 2-ethylhexylacrylate (25.0g, 135.7 mmole) were purged with nitrogen for 15 min then heated to 175°C. for 10 hours. The following table showed the conversion and molecularweighs of the polymer.

Sample Time (mins.) Mn Mw Conversion 1 40 1006 1117 24.2 2 90 1446 169942.0 3 150 1750 2241 51.9 4 600 2185 3115 98.9

Example 9 Polymerization with s,s′-bis-(α,α′-disubstituted-α″-aceticacid) trithiocarbonates

Procedure:

The trithiocarbonate was used as inifertor to make polystyrene. Thetrithiocarbonate (2.0 g, 7.1 mmole) and styrene (25 g, 240.4 mmole) with1 ml decane as internal standard were polymerized at 140° C. undernitrogen for 6 hours. The following table showed the progress of thepolymerization.

Sample Time (mins.) Mn Mw Conv. % 1 30 613 648 9.5 2 60 779 831 16.9 3120 1829 2071 53.9 4 300 2221 2559 72.3 5 360 2537 2956 84.5

Example 10 Polymerization with s,s′-bis-(α,α′-disubstituted-α″-aceticacid) trithiocarbonates

Procedure:

The trithiocarbonate was used as chain-transfer agent to make blockcopolymers of 2-ethylhexylacrylate and styrene. The trithiocarbonate(1.5 g, 5.3 mmole), 2-ethylhexylacrylate (30 g, 162.8 mmole) and AIBN(0.03 g, 0.18 mmole) with 1 ml undecane as the internal standard werepolymerized at 60° C. under nitrogen as before. 6.5 hours later, styrene(15 g, 144.2 mmole) and AIBN (0.03 g, 0.18 mmole) was added. Thepolymerization continued and the following shows the progress.

Sample Time (mins.) Mn Mw Conv. % 1  70 1922 2459 32.5 2 135 3556 420480.8 3 270 4095 4874 95.0 4  330* 4407 5025 96.6 5 1290  4834 5969 —*Styrene added

Example 11

Polymerization with the trithiocarbonate from example 3. Thetrithiocarbonate (1.82 g. 5 mmole), n-butyl acrylate (25 g, 195.1 mmole)and AIBN (0.04 g, 0.25 mmole) with 1 ml undecane as the internalstandard were polymerized under nitrogen atmosphere for 7 hours. Itshowed 97.5% conversion by GC as depicted in the following table:

Sample Time (min) Mn Mw Pd % Conv. 1 60 2177 2792 1.26 46.2 2 120 27583865 1.40 67.1 3 420 3786 5439 1.44 97.5

While in accordance with the patent statutes the best mode and preferredembodiment have been set forth, the scope of the invention is notlimited thereto, but rather by the scope of the attached claims.

1. A composition comprising: a polymer represented by the formula:

where R¹ and R², independently, represent an alkyl having from 1 to 6carbon atoms, a substituted C₁ to C₆ alkyl having one or moresubstituents, one or more aryls, a substituted aryl having from 1 to 6substituents on the aryl ring; wherein said substituents, independently,are selected from an alkyl having from 1 to 6 carbon atoms, an aryl, ahalogen which can be the same or different, a cyano, an ether having atotal of from 2 to 20 carbon atoms, a nitro, and combinations thereof;or wherein R¹ and R² are part of a cyclic ring having from about 5 toabout 12 total carbon atoms; and wherein said repeat group ispolymerized from said at least one conjugated diene monomer having atotal of from 4 to 12 carbon atoms, and wherein said at least one vinylmonomer is represented by the repeat unit:

wherein R³ represents hydrogen, halogen, C₁-C₄ alkyl, and substitutedC₁-C₄ alkyl, wherein said substituents, independently, are selected fromone or more hydroxy, alkoxy, aryloxy(OR⁵), carboxy, acyloxy,aroyloxy(O₂CR⁵), alkoxy-carbonyl(CO₂R⁵), and aryloxy-carbonyl; whereinR⁴ represents hydrogen, R⁵, CO₂H, CO₂R⁵, COR⁵, CN, CONH₂, CONHR⁵, O₂CR⁵,OR⁵ and halogen; and wherein R⁵ represents C₁-C₁₈ alkyl, substitutedC₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, aralkyl, and alkaryl, and whereinsaid substituents, independently, represent one or more epoxy, hydroxy,alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts),alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo ordialkylamino; and wherein m and n, independently, are from about 1 toabout 10,000.
 2. A composition according to claim 1, wherein R¹ and R²,independently, are selected from said alkyl, said substituted alkylhaving one or more substituents, said one or more aryls, saidsubstituted aryl having one or more substituents, and combinationsthereof.
 3. A composition according to claim 2, wherein R¹ and R², isindependently, methyl or phenyl, and wherein m is from about 5 to about500, and n is from about 5 to about
 500. 4. A composition according toclaim 1, wherein said m repeat group and said n repeat group ispolymerized, independently, from said one or more monomers which is anacrylate having from 1 to 8 carbon atoms, a methacrylate having from 1to 8 carbon atoms, styrene, butadiene, isoprene, or acrylonitrile, andcombinations thereof, and wherein m is from about 10 to about 200, andwherein n is from about 10 to about
 200. 5. A composition according toclaim 1, wherein the polydispersity of said polymer is 1.75 or less. 6.A composition according to claim 2, wherein the polydispersity of saidpolymer is 1.75 or less.
 7. A composition according to claim 3, whereinthe polydispersity of said polymer is 1.50 or less.
 8. A compositionaccording to claim 4, wherein the polydispersity of said polymer is 1.50or less.
 9. A composition comprising: a polymer having the formula:

where R¹ and R², independently, represent an alkyl having from 1 toabout 6 carbon atoms, a substituted C₁ to about C₆ alkyl having one ormore substituents, one or more aryls, and a substituted aryl having from1 to 6 substituents on the aryl ring; wherein said one or moresubstituents, independently, represent an alkyl having from 1 to 6carbon atoms, an aryl, a halogen which can be the same or different, acyano, an ether having a total of from 2 to about 20 carbon atoms, anitro, and combinations thereof; or wherein R¹ and R² are part of acyclic ring having from about 5 to about 12 total carbon atoms; andwherein said repeat group is polymerized from said at least oneconjugated diene monomer having a total of from 4 to 12 carbon atoms,and wherein said at least one vinyl monomer is represented the repeatunit:

wherein R³ represents hydrogen, halogen, C₁-C₄ alkyl, and substitutedC₁-C₄ alkyl wherein said substituents, independently, represent one ormore hydroxy, alkoxy, aryloxy(OR⁵), carboxy, acyloxy, aroyloxy(O₂CR⁵),alkoxy-carbonyl(CO₂R⁵), and aryloxy-carbonyl; wherein R⁴ representshydrogen, R⁵, CO₂H, CO₂R⁵, COR⁵, CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵ andhalogen; and wherein, R⁵ represents C₁-C₁₈ alkyl, substituted C₁-C₁₈alkyl, C₂-C₁₈ alkenyl, aryl, aralkyl, and alkaryl, and wherein saidsubstituents, independently, represents one or more epoxy, hydroxy,alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts),alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo anddialkylamino, and wherein m and n, independently, are from about 1 toabout 10,000, and wherein E is XR′, where R′, independently, representsH, C₁-C₁₈ alkyl, a substituted C₁-C₁₈ Alkyl; wherein said substituent isselected from halogen, hydroxyl, alkoxy, C₁-C₁₈ hydroxyalkyl, and aC₁-C₁₈ aminoalkyl, and X represents oxygen, sulfur, NH, and NR′; orwherein E is

wherein R⁶ through R⁹, independently, represent H, C₁-C₁₈ alkyl, aryl, asubstituted aryl having from 1 to 6 substituents on the ring, whereinsaid substituent is selected from halogen, hydroxyl, or alkoxy, C₁-C₁₈hydroxy alkyl, C₁-C₁₈ amino alkyl, and C₁-C₁₈ mercapto alkyl, andwherein Y represents oxygen, sulfur, NH, and NR⁶; or wherein E is OR¹⁰where R¹⁰ represents an alkyl having from 1 to 18 carbon atoms, and asubstituted alkyl having from 1 to 18 carbon atoms, wherein saidsubstituent is selected from halogen, hydroxyl, alkoxy, a hydroxy alkylhaving from 1 to 18 carbon atoms, an amino alkyl having from 1 to 18carbon atoms, and combinations thereof; or combinations thereof.
 10. Acomposition according to claim 9, wherein R¹ and R², independently, aresaid alkyl, or said substituted alkyl having one or more substituents,or said one or more aryls, or said substituted aryl having one or moresubstituents, or combinations thereof.
 11. A composition according toclaim 10, wherein R¹ and R², are independently, methyl or phenyl, andwherein m is from about 5 to about 500, and n is from about 5 to about500.
 12. A composition according to claim 10, wherein R³ said m repeatgroup and said n repeat group is, polymerized, independently, from saidone or more monomers which is an acrylate having from 1 to 8 carbonatoms, a methacrylate having from 1 to 8 carbon atoms, styrene,butadiene, isoprene, or acrylonitrile, or combinations thereof, andwherein in is from about 10 to about 200, and wherein n is from about 10to about
 200. 13. A composition according to claim 9, wherein thepolydispersity of said polymer is 1.75 or less.
 14. A compositionaccording to claim 10, wherein the polydispersity of said polymer is1.75 or less.
 15. A composition according to claim 11, wherein thepolydispersity of said polymer is 1.50 or less.
 16. A compositionaccording to claim 12, wherein the polydispersity of said polymer is1.50 or less.